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OPEN Reduced graphene oxide supported

MXene based metal oxide
ternary composite electrodes
for non‑enzymatic glucose sensor
applications
Tamil Selvi Gopal 1, Khalid E. Alzahrani 2,3, Abdulaziz K. Assaifan 2, Hamad Albrithen 2,3,
Abdullah Alodhayb 2,3, Muthumareeswaran Muthuramamoorthy 2, Saravanan Pandiaraj 4 &
Andrews Nirmala Grace 1*

Diagnosis and monitoring of glucose level in human blood has become a prime necessity to avoid
health risk and to cater this, a sensor’s performance with wide linearity range and high sensitivity
is required. This work reports the use of ternary composite viz. MG–Cu2O (rGO supported MXene
sheet with ­Cu2O) for non-enzymatic sensing of glucose. It has been prepared by co-precipitation
method and characterized with X-ray powder diffraction, Ultraviolet–visible absorption spectroscopy
(UV–Vis), Raman spectroscopy, Field emission scanning electron microscopy, High resolution
transmission electron microscopy and Selected area diffraction. These analyses show a cubic
structure with spherical shaped ­Cu2O grown on the MG sheet. Further, the electrocatalytic activity
was carried out with MG–Cu2O sensing element by cyclic voltammetry and chronoamperometry
technique and compared with M–Cu2O (MXene with ­Cu2O) composite without graphene oxide. Of
these, MG–Cu2O composite was having the high defect density with lower crystalline size of ­Cu2O,
which might enhance the conductivity thereby increasing the electrocatalytic activity towards the
oxidation of glucose as compared to M–Cu2O. The prepared MG–Cu2O composite shows a sensitivity
of 126.6 µAmM−1 ­cm−2 with a wide linear range of 0.01to 30 mM, good selectivity, good stability over
30 days and shows a low Relative Standard Deviation (RSD) of 1.7% value towards the sensing of
glucose level in human serum. Thus, the aforementioned finding indicates that the prepared sensing
electrode is a well suitable candidate for the sensing of glucose level for real time applications.

As per the World Health Organization (WHO) survey, a drastic increase in diabetics has made it as the 7th
most deadliest and life-threatening disease in the w ­ orld1,2, which is due to the insufficient amount of insulin in
human body. In order to avoid this, periodic and continuous monitoring of glucose level (in human blood or
tear or saliva or acetone level in breathing air) is necessary and is done by painless method such as non-invasive
or closed loop t­ echnique3,4. Further economical and efficient sensors are required to be replaced with the cur-
rently available high-cost sensor in the market, which are enzymatic based leading to high cost, poor stability
and reproducibility in the m ­ easurements5. An aforementioned issue with the enzymatic sensor is due to the
denaturation of enzymes with temperature, pH and humidity 6. In order to resolve the pre-existing problems,
huge effort is made by the researchers to develop enzyme free glucose sensors by direct oxidation of glucose mol-
ecule on the surface of the sensing electrode using metal or metal alloys as a sensing element (Pt, Pd, Au, Pt–Au,
Ni–Cu, Pt–Pd and Ni–Cu)7–9. Even though it resolves the enzymatic sensor drawbacks, it still lacks in terms of
production cost, selectivity and slow kinetic mechanism during glucose ­oxidation10. In order to overcome the
above-mentioned issues, researchers are focusing on various new electrode materials especially metal oxides

1
Centre for Nanotechnology Research, Vellore Institute of Technology, Vellore, Tamil Nadu, India. 2Present address:
Biological and Environmental Sensing Research Unit, King Abdullah Institute for Nanotechnology, King Saud
University, P.O. Box 2455, Riyadh 11451, Saudi Arabia. 3Department of Physics and Astronomy, College of Science,
King Saud University, Riyadh 11451, Saudi Arabia. 4Department of Self‑Development Skills, CFY Deanship, King
Saud University, Riyadh, Saudi Arabia. *email: [email protected]

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(MO) as a sensing element instead of metal-based electrodes. Various MOs such as CuO, C ­ u2O, ­Co3O4, NiO, and
­Fe2O3 have been investigated as alternative sensing ­elements11–16. Among the different metal oxides, copper-based
metal oxide shows good catalytic activity towards glucose sensing for non-enzymatic sensor. But a lagging of
sensing parameters such as sensitivity or linearity is observed and to avoid such lagging of sensing parameters,
the active surface area or surface to volume ratio of the sensing elements has to be improved by fine tuning the
size, shape, faces or with the use of composites with carbon-based materials and Cu/Cu2O heterostructures. Such
reported investigations are listed in Table S1 and from the table, it’s clear that these kind of variations improve
the sensitivity but not the linearity range of the sensor, which is also a prime requirement for diabetic patients.
Low conductive nature of single metal oxide may hinder the flow of electrons between the catalyst and
electrode, which will further reduce the sensing performance of non-enzymatic glucose sensors. To cater this,
highly conductive materials in combination with metal oxide as a binary or ternary or multi compound-based
composites have been proposed 17. Various works on metal with MO (Pt/CuO, ­Co3O4@Pt@MnO2, Au/CuO,
NiO–Au) 18–22, MO with MO ­(Co3O/NiO, ZnO/NiO, CuO/Cu2O, CuO/ZnO), ternary MO (Mn–Cu–Al), 23–27
carbon materials with metal oxide composites (CuO/rGO, ­Cu2O/rGO, NiO/rGO, NiCo@f–MWCNT, MWCNT/
Fe3O4)28–32 have been studied as non-enzymatic glucose sensing elements. Among all these, reduced graphene
oxide (rGO) based composites possess fast electron transfer ability during the oxidation of glucose due to its
highly conductive nature, high surface area and good corrosion properties. In addition, composite of rGO with
metal oxides improves the stability of the electrode as compared to other combinations. Zeng et al., prepared
nickel oxide decorated reduced graphene oxide sheet for sensing of glucose molecules, which has shown a higher
response as compared to bare NiO with a linear range of 0.005 to 4.5 mM. rGO sheets in the composite prevent
the growth of clustered nanoparticles thereby enhancing the electron transfer ability between the catalyst and
­electrode33. Phetsang et al. prepared copper based rGO composites film for glucose sensing application. The
prepared film showed a sensitivity of 172 µAmM−1 ­cm−2 with a linear range of 0.1 to 12.5 mM. Recently, Liu
et al. prepared a three-dimensional metal oxide/metal/reduced graphene oxide complex as a sensing element.
The prepared complex showed a higher response as compared to bare C ­ u2O with a linear range of 16.65 mM
of glucose ­concentration34. Similar process was reported in various literatures in which different combination
of rGO with metal oxides have been studied to improve the sensing performance of non-enzymatic glucose
­sensor17,35–38. Although these composites have improved the sensitivity as compared to bare metal oxides, it still
needs a lot of improvement in the linear range with high sensitivity to make it commercially viable.
Recently, a new 2D material called MXene has been explored widely as an alternative to graphene and such
materials are shown to be good for sensing applications typically in the linearity range. Among the different
MXenes, titanium carbide ­(Ti3C2Tx) has shown to be the best supporting material for electrochemical sensors
due to its biocompatibility, high surface area, high porosity, high conductivity as well as the presence of a large
number of functional groups on the MXene s­ heet39–41. These properties of T ­ i3C2Tx sheet helps to construct the
best supporting material in the composites as compared to reduced graphene oxide for the preparation of non-
enzymatic biosensors. Rakhi et al. prepared Au/Ti3C2Tx based composite for sensing glucose molecules with a
wide linear range of 0.1 to 18 ­mM42. Chen et al. prepared Ce-metal organic framework with ­Ti3C2Tx composite
for the sensing of L-Tryptophan and reported a wide linear range (0.2 to 139 µM) as compared to the carbon-
based composites. As similarly, in our previous study, metal oxide ­(Cu2O) with ­Ti3C2Tx composites was shown
to possess a broad linear range (0.01 to 30 mM) of glucose sensing with a good ­stability43. However, a number of
works have been reported on the synthesis of composites with metal oxide, which suffer in terms of low sensi-
tivity due to restacking or internal sheet aggregation, which in turn limits the access of target molecules during
the electrochemical process. To prevent this, different strategies have been explored like introduction of foreign
atoms or incorporating carbon-based materials in the MXene based composite s­ tructure44–47.
Based on these concerns, this work is focused on the preparation of C ­ u2O/rGO/Ti3C2Tx composite-based
sensing elements by co-precipitation method. Further, the prepared material was characterized using XRD,
Raman Spectroscopy, FE-SEM, HR-TEM and UV–Visible spectroscopy. The sensing element was fabricated
as electrode probe and further employed to investigate the sensing of glucose using chronoamperometry (CA)
technique.

Experimental methods
Chemicals and reagents. Graphite (325 mesh size), potassium permanganate ­(KMnO4), copper (II) ace-
tate hydrate (Cu ­(CH3COO)2·H2O), fructose ­(C6H12O6), sucrose ­(C12H22O11), L-ascorbic acid ­(C6H8O6), sodium
hydroxide (NaOH), sodium chloride (NaCl), potassium chloride (KCl), urea ­(CH4N2O), uric acid ­(C5H4N4O3)
and D-glucose ­(C6H12O6) were purchased from Sigma Aldrich and the MAX phase was purchased from Fors-
man. Hydrofluoric acid (HF), sulfuric acid (­ H2SO4), hydrogen peroxide (­ H2O2), ethanol (­ C2H5OH) and dime-
thyl sulfoxide (DMSO) were purchased from SD Fine Chem Ltd. All the chemicals are of AR grade and utilized
as it is without any further purification.

Synthesis and fabrication of sensing electrode. Preparation of graphene oxide (GO). The prepara-
tion of GO was carried out by modified Hummer’s method as per the previous r­ eports47,48 with a slight modifica-
tion. In brief, 2 g of graphite powder was added to 100 ml of ­H2SO4 and stirred for 30 min. The mixed graphitic
solution was then transferred to ice-bath and then 12 g of ­KMnO4 was added slowly. After 2 h, the solution was
removed from ice bath and stirred at room temperature (RT) for 2 h. After this, 200 ml of ice water was added
gradually and then heated at 50 °C for 2 h. After heating, the solution was kept to cool down to RT and then
600 ml of DI water was added slowly. Finally, 10 ml of ­H2O2 was added to it and stirred overnight. The obtained
solution was further washed with DI water until the supernatant becomes neutral. The solid was transferred to
petri dish and dried at.

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Figure 1.  A schematic showing the synthesis process of MG–Cu2O composite.

Preparation of MXene and MG composites. The conversion of MAX phase to MXene was carried out as similar
to our earlier r­ eport43 and the preparation of MG composite is given in Fig. 1 (step 1 and 2). The formed MXene
was used for the preparation of MG composites by hydrothermal method. Initially, 100 mg of MXene was added
to 90 ml of DI water and then sonicated for 30 min labeled as solution A. Similarly, 100 mg of GO was added
into 90 ml of DI water and then sonicated for 30 min and named as solution B. The prepared solution B was
added into solution A and sonicated for 1 h. After this, the mixed solution was transferred to 250 ml Teflon lined
stainless steel autoclave and heated at 90 °C for 12 h. After that, the solution was cooled down to RT, the obtained
solution is further centrifuged and washed with DI water several times. Finally, the formed rGO–MXene solid
was dried at 60 °C and named as MG-100. Likewise, different weight ratio of graphene oxide in solution B was
varied with a fixed amount of MXene (100 mg) for the preparation of MG composite and named as MG-0,
MG-25, MG-50 and MG-75 respectively.

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Preparation of C­ u2O‑rGO‑MXene composite. The synthesis process of ­Cu2O–rGO–MXene composite is given

in Fig. 1 (step 3). To 100 mg of the prepared MG-50 composites, 1 g of copper (II) acetate hydrate and 1.8 g of
D-Glucose was added to 100 ml of DI water and sonicated for 1 h. The mixed complex solution was further
stirred at RT for 12 h. After this, the solution was transferred to an oil bath and heated at 90 °C for 5 h. The
obtained product was further washed with DI water and ethanol for 5 times and then dried at 60 °C overnight
and labeled as MG–Cu2O. Bare MXene–Cu2O composite was prepared as similar to the earlier report for com-
parison and labeled as M–Cu2O 43.

Characterization and electrochemical measurements of sensing materials. The formation of

MG composite and crystallinity of C ­ u2O–rGO–MXene composite were confirmed with XRD (D8 Advance from
Bruker, Cu Kα radiation) and Raman spectroscopy (512 nm laser—HORIBA). UV–Visible absorption spectrum
was carried out with JASCO (V-670 PC) to examine the optical behavior of the prepared samples. The morphol-
ogy and particle distribution of ­Cu2O nanoparticles on the rGO and MXene sheet in the composite was analyzed
with FE-SEM (Thermo Fisher FEI Quanta 250 FEG) and HR-TEM (FEI-Tecnai G2 20 Twin). All the electro-
chemical measurements were carried out with CHI-600C workstation.

Preparation of sensing electrode. Cu2O–rGO–MXene composite electrode was fabricated by drop cast-
ing method. Initially, the glassy carbon electrode was cleaned with A
­ l2O3 powder and then washed with ethanol,
acetone followed by DI water and the washed electrode was further dried under ­N2 gas. For the deposition of the
prepared composite, a mixture of 1 mg MG–Cu2O, 0.045 ml of DI water and 0.005 ml of 5% nafion solution was
sonicated for 30 min and then 5 µl of mixed solution was dropped on the dried electrode. Further the dropped
electrode was left overnight at room temperature for drying. In the same way, MG composite and M–Cu2O
composites-based electrodes were prepared and then further used for studying the sensing performance.

Results and discussion

Structural analysis of bare and composites. The conversion of MAX phase to MXene, MG and MG–
Cu2O composite formation process is given in Fig. 1. To confirm the formation of the material, structural and
phase analysis were carried out with XRD and Raman spectroscopy. For the bare MXene (MG-0), the disap-
pearance of 38.92° peak (Al peak) as well as a shift of (002) peak from 9.54° to ~ 6.4° confirms the formation
of MXene from MAX phase as given in Figs. 2a, S1 ­respectively49. The XRD of the prepared MG composite at
different loadings of graphene oxide (25 to 100% of GO) is given in Fig. S1. The broadening of (002) peak as well
as a shift from ~ 6.4° to ~ 8.8° and appearance of rGO peak at 25.35° confirms the formation of reduced graphene
oxide with MXene c­ omposite50. As the loading amount of graphene oxide increases from 25 to 100%, an incre-
ment in the intensity of reduced graphene oxide peak as well as the clamp down of MXene peaks are observed.
The corresponding d-spacing values of MXene sheet in the MG composites are 13.8 Å (MG-0), 10.14 Å (MG-
25), 9.98 Å (MG-50), 10.37 Å (MG-75) and 10.1 Å (MG-100) respectively.
For the MG–Cu2O composite, XRD peaks are observed at 2θ values of 29.5°, 36.4°, 42.3°, 61.3° and 73.5°
respectively matching with the JCPDS (Joint Committee on Powder Diffraction Standards) card number 05–0667
with cubic ­Cu2O43 and the corresponding faces are (110), (111), (200), (220) and (311). The obtained XRD peak
of ­Cu2O in the composite is similar to bare C ­ u2O but the broadening of peak is observed, which indicates the
reduction of crystalline size in the composite (14.33 nm) as compared to bare (35.69 nm).
To understand the functional groups and confirmation of the reduction of graphene oxide to reduced
graphene oxide, FTIR analysis was done and given in Fig. S4. A broad frequency range observed around
3200–3650 ­cm−1 is related to the –OH stretching vibration. For ­Ti3C2Tx, graphene oxide and ­Cu2O, a peak at
2985 ­cm–1 (C–H stretching of methylene), 2894 ­cm−1 (C–H stretching of methyl functional group), 1724 ­cm−1
(C=O stretching), 1620 ­cm−1 (C=C), 1045 ­cm−1 (stretching vibration of epoxy bond (C–O bond)), 947 ­cm−1
(C–F) and 620 or 626 ­cm−1 (Cu–O stretching vibration of ­Cu2O) was observed. For the composites (rGO–Cu2O,
MG–Cu2O), the disappearance of C–O peak confirms the reduction of graphene oxide to reduced graphene oxide
and highlighted in Fig. S449. The conversion of GO to rGO occurs due to the presence of glucose in the reaction
system, which acts as a reducing agent for both GO as well as for C ­ u2O during its s­ ynthesis49,72. In order to find the
defect density of carbon material in the composites and confirmation of un-oxidized MXene in the composites,
the material was studied with Raman spectroscopy (Figs. 1b, S2a and S2b). From Figs. 2b, S2a, peaks at 158, 288,
417 and 608 ­cm−1 are related to the in-plane vibration of Ti–C bond (­ Eg mode), surface terminal groups (–OH)
and the out-plane vibration of Ti–C bond (­ A1g mode), r­ espectively51. Along with these, two additional peaks are
also observed for MG composites and are related to the D-band (1350 ­cm−1) and G- band (1580 ­cm−1) of rGO as
given in Fig. S2b52,53. A variation in the I­ D/IG ratio is observed with an increment in the loading amount of GO,
which is in the order of MG-50 (1.055) > MG-100 (1.038) > MG-75 (1.032) > MG-25 (0.827). A higher disorder
intensity is observed for MG-50 composite due to the strong interaction or bonding between reduced graphene
oxide and MXene sheet as compared to other c­ omposites49,54,55.
For MG–Cu2O, the combined peaks of Eg mode (Ti–C) of MXene, D-band and G-band of reduced graphene
oxide and Cu–O vibrations (214 ­cm−1 (2Eu) and 628 ­cm−1 (Tu1)) are observed. It is worth to notice that there
is absence of T­ iO2 (142 ­cm−1) peak, which signifies that MXene sheet in composites are not o ­ xidized43. Further,
the optical properties of bare and composites were studied with UV–Vis spectroscopy as given in Figs. 2c, S3a,c.
From Fig. S3a, a strong adsorption band is noticed in the UV region of MXene and MG-50 composites, which
is in agreement with the previous reported l­ iteratures56. It is related to the –OH functional group on the sheets,
which leads to the bandgap formation of MXene (1.2 eV) and MG-50 composites (1.28 eV)56,57. From Figs. 2c,
S3c, a red shift of the adsorption edge is observed for MG–Cu2O composite (~ 678 nm) as compared to the ­Cu2O
(~ 635 nm) and M–Cu2O (~ 646 nm) composite.

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Figure 2.  (a) X-ray diffraction patterns of synthesized ­Cu2O, ­Ti3C2Tx, MG (50% of GO) and MG–Cu2O
composite (b) Raman spectra for ­Cu2O, MXene, and their composites (c) Optical absorption spectra of M–
Cu2O, MG–Cu2O and (d) Optical band gap for M–Cu2O, MG-Cu2O.

The corresponding bandgap of material is obtained from the Tauc plot and is given in Figs. 2d, S3d. The
bandgap values are 1.78 eV (MG–Cu2O), 1.87 eV (M–Cu2O) and 1.9 eV ­(Cu2O) respectively. The above findings
suggest the formation of active heterojunction between the MG and ­Cu2O interface as well as a strong electron
conduction of graphene in the MG–Cu2O ­composite58. As per the structural analysis through XRD, Raman and
UV–Visible spectroscopy, a low d-spacing and high defect density of MG-50 composite lead to high conductiv-
ity as compared to MG-0, MG-25, MG-75 and MG-100 respectively. A low value in the crystallite size and a red
shift in the adsorption edge of C
­ u2O in the composite may lead to more active sites as compared to bare ­Cu2O.

Morphological study of bare materials and composites. Morphological study of MAX phase,
MXene, MG-50 and MG–Cu2O composites were done with FE-SEM and given in Figs. S5 and 3. After HF etch-
ing of the MAX phases (Fig. S5a,b), a spacing between the layers are observed as similar to the accordion like
structure and is given in Fig. S5c,d. This formation is one more evidence for MXene conversion as supported
with the result of XRD (a shift of (002) peak from 9.54° to ~ 6.4° and disappearance of 38.92° peak). After soni-
cation and hydrothermal treatment of MXene and graphene oxide sheets, the formed reduced graphene oxide
sheets are crevice and cover the MXene sheets 44 (highlighted in green—Fig. 3a,b). It reveals that the two materi-
als are well attached leading to the formation of MG ­composites59.
For the MG–Cu2O composite (Fig. 3c,d), a non-uniform distribution of aggregated ­Cu2O nanoparticles
are ornamented on the surfaces of MG-50 composite. These particles are spherical in shape with the size of
500–700 nm. To confirm the role of rGO sheet in the morphological changes, a MG–Cu2O composite is prepared
without rGO sheet (M–Cu2O) and analyzed with FE-SEM. In the absence of reduced graphene oxide sheet, an
octahedron shape of ­Cu2O (size of 1.5 µm) is formed and highlighted in red circle in Fig. S6a. In contrast, a
spherical shape (Figs. 3d, S6b) of C
­ u2O (size of 500–700 nm) is formed for MG–Cu2O composite. In the presence

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Figure 3.  FE-SEM images at different magnifications (a, b) MG-50 and (c, d) MG-Cu2O composite.

of rGO sheet, the preclusion of restacking the MXene sheets maintain the larger surface area of sheets as well as
the ample amount of functional groups on the surface and edges of sheet may hinder the nanoparticle agglom-
eration leading to the formation of spherical shape of ­Cu2O in the MG–Cu2O composite as given in Fig. S6b
(marked in red circle). In order to understand the distribution of C ­ u2O nanoparticles (MG–Cu2O), HR-TEM
was done and given in Fig. 4a,b. A larger number of nanoparticles are embedded on the surface as well as edges
of sheets as observed from Fig. 4b. The average sizes of the distributed nanoparticles are ~ 4.96 ± 1.9 nm and the
respective histogram plot is given in Fig. 4c. Further, the nature of distributed nanoparticles is studied with the
help of SAED pattern for MG–Cu2O composite (Fig. 4d). It shows five different rings along with different spots
indexed with (111), (200), (211), (220) and (311), which are well matching the XRD results.

Electrochemical properties of bare and composite electrodes. In order to find out the highest
electron transfer rate capability of GO loaded MG composites (MXene, MG-25, MG-50, MG-75 and MG-100),
cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques were investigated
in 0.1 M KCl with 5 mM of [Fe(CN)6]4−/3− electrolyte (Fig. S7a–d). As observed from the figure, both anodic
and cathodic peaks are observed in cyclic voltammetry profile of all the materials with the potential difference
(ΔEvp) of 395 mV (MXene), 275 mV (MG-25), 179 mV (MG-50), 233 mV (MG-75) and 250 mV (MG-100)
respectively. Of the various composites, 50 wt% of graphene oxide loaded MG composite (MG-50) shows a lower
ΔEvp as compared to other materials, which indicates the high electron transfer rate as compared to ­others60.
An increment in graphene oxide loading may reduce the active electrochemical surface area and hinder the flow
of electrons, which is further confirmed with the charge transfer resistance value (Rct) between the modified
electrode and electrolyte for these materials.
For obtaining this, an electrochemical impedance spectral analysis was carried out in the same medium and
given in Fig. S7b,d. For all the wt% of graphene oxide loaded MG composites, the graph shows a semicircle along
with straight-line in the high frequency region. The diameter of the semicircle is equivalent to the charge transfer
resistance ­value61. The obtained values for Rct are 80 kΩ (MXene), 110 kΩ (MG-25), 0.25 kΩ (MG-50), 1.46 kΩ
(MG-75) and 20 kΩ (MG-100) respectively. A low charge transfer value for MG-50 composite indicates the high
electron transfer rate capability as compared to the other loading, which might be due to its low d-spacing and
highest defect density of the prepared material MG-50.
Further, MG-50 composite has been chosen for the preparation of ternary composites (MG–Cu2O compos-
ites). A cyclic voltammetry and electrochemical impedance spectra analysis of M–Cu2O (Fig. S7e,f), MG-50
and MG–Cu2O composite is given in Fig. 5a,b. The addition of ­Cu2O catalyst to MG-50 enhances its anodic and
cathodic current as compared to MG-50 alone. A comparative plot of the voltage difference between redox peak
(ΔEvp) and charge transfer resistance ­(Rct) for the different MG composites, M–Cu2O and MG–Cu2O are given in
Fig. 5c,d. From this plot, a low ΔEvp (121 mV) and ­Rct (0.1 kΩ) value was observed for MG–Cu2O, which might
be due to its interconnected structure of ­Cu2O with rGO and MXene sheets as supported with FE-SEM image

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Figure 4.  (a, b) HR-TEM images of MG-Cu2O composite with different magnification (Pink and blue
circle shows the ­Cu2O on the edges of MXene and rGO sheet, the yellow arrow shows the rGO sheets in the
composites and red arrow indicates the MXene sheet) (c) size distribution of C
­ u2O nanoparticles on MXene
sheet (d) selected area electron diffraction (SAED) pattern of MG-Cu2O composite.

(Fig. 3c,d). In order to understand the charge transfer mechanism, the diffusion studies was further performed
for MG–Cu2O composite by tracing the peak current response with changing scan rates from 10 to 100 mV/s
(Fig. 6a). A linear response is observed for peak currents with respect to the square root of scan rate, which
­ rocess62.
indicates that the rate of the reaction is a diffusion-controlled p

Electrocatalytic study of bare and composites electrode. In order to verify the above-mentioned
results, cyclic voltammetry study of MXene, MG-25, MG-50, MG-75 and MG-100 was carried out in 0.1 M
NaOH in the presence of glucose and given in Fig. 6b. A higher current variation is observed for MG-50 com-
posite as compared to others, which implies the faster electron transfer between the electrode and sensing ele-
ment during the oxidation of glucose. Further, the role of rGO and ­Cu2O in MXene based composite is studied
and given in Fig. 6c. No variation in the current is observed in the absence of glucose analyte for MG-50, M–
Cu2O and MG–Cu2O respectively. With the addition of 5 mM glucose, instantaneous enhancement in the cur-
rent was observed for all the materials, which signifies that all the prepared materials can act as a sensing element
for glucose sensor. Among the composites, a huge enhancement was observed when bare M–Cu2O is replaced
with MG–Cu2O (Fig. 6c). There is a presence of anodic peak in the potential range of 0.4 to 0.8 V, which occurs
due to the oxidation of copper ion in the electrode during the sensing of glucose molecule as explained in Fig. 7.
Briefly, in the presence of glucose, C­ u+ ions are oxidized to C­ u2+ with the release of electrons into the solutions
and the formed C ­ u2+ ions are further oxidized to C
­ u3+ ions. These processes initiate the oxidation of glucose and
simultaneously there is a reduction of ­Cu3+ to ­Cu2+ resulting in an enhancement of current. Further, the formed
gluconolactone gets converted to gluconic acid at 0.6 V via the hydrolyzation ­process63. In the composite, rGO
prevents the stacking of MXene sheet, which improves electron transfer rate with more active sites. This may
enhance the peak and spike current of MG–Cu2O composite, indicating more C ­ u3+ ion formation for MG–Cu2O

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Figure 5.  (a) Cyclic voltammetry comparison of MG-50 and MG-Cu2O composites in 5 mM Fe (CN)3-/4- along
with 0.1 M KCl (b) Nyquist plot of MG-50 and MG-Cu2O composites with the frequency range of 1 MHz to
0.1 Hz (c) 3D bar graph of potential difference between redox peak (ΔEvp) for different materials and (d) 3D bar
graph of charge transfer resistance (­ Rct) for different materials.

composite as compared to M–Cu2O. As the concentration of glucose increases, a spike and peak current of
MG–Cu2O modified electrode increases. It shows that the prepared composite is electrochemically active and
responding well during the oxidation of glucose. Therefore, the replacement of M–Cu2O to MG–Cu2O compos-
ite has enhanced the glucose oxidation current beneficiary for sensor applications.
To reinforce the above-mentioned result (CV analysis), a chronoamperometry (CA) analysis of M–Cu2O and
MG–Cu2O composite was carried out in 0.1 M NaOH at different concentrations of glucose (Fig. S8a). As the
concentration of glucose increases, a huge improvement in current for MG–Cu2O (Figs. 6d, S8a) was observed
as compared to M–Cu2O. Therefore, results show that the replacement of M–Cu2O with MG–Cu2O increases
the conductivity of the sensing element and improves the active sites for sensing analyte.

Sensing performance of modified electrode. In order to determine the suitable working potential of
MG–Cu2O, CA study was further carried out with the addition of 0.1 mM glucose in 0.1 M NaOH at various
bias voltages (0.5, 0.6 and 0.7 V). The corresponding current response is plotted with respect to concentration of
glucose and given in Fig. S8b. An increment in the current is observed with an increase in the concentration of
the glucose at all the biasing conditions. Among all the bias, a high change in the current was observed at 0.6 V
and hence this potential was kept constant for further study. The sensitivity of MG–Cu2O modified electrode
was obtained using CA technique with the stepwise addition of glucose at every 50 s (Fig. 8a). A quick change
in current (less than 5 s) was observed with the addition of glucose to the electrolyte. A magnified image at the
lowest concentration of glucose and the respective changes in current is provided in the inset of Fig. 8a. Even
for the lower concentration (10 µM), there is an enhancement in the current. Later, a linear plot of current vs.
concentration of glucose is obtained as given in Fig. 8b. Similarly, M–Cu2O (Fig. 8b) and rGO–Cu2O (Fig. S9a)
composites were studied and the corresponding current response with respect to the change in concentration is
given in Figs. 8c, S9b respectively. MG–Cu2O composite shows a wider linear range as compared to rGO–Cu2O
composites whereas it is similar as M–Cu2O composite. However, a tenfold increment of current is observed by
the replacement of M–Cu2O with MG–Cu2O during the sensing of glucose molecules. It might be due to the

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Figure 6.  (a) Peak current vs. square root of scan rate for MG-Cu2O composite and the inset—cyclic
voltammetry (0.1 M of KCl + 5 mM of Fe (CN)3−/4−solution) at different scan (b) CV response of MG composite
with varying the weight ratio of MXene and Graphene oxide in the presence of 5 mM glucose (in 0.1 M NaOH)
(c) CV curve of MG-50, M-Cu2O and MG-Cu2O composite at 0 and 5 mM glucose (in 0.1 M of NaOH) and (d)
CV of MG-Cu2O composite at different concentrations of glucose in 0.1 M NaOH.

lowest d-spacing and highest defect density of the prepared structure as well as the introduction of rGO, which
avoids the restacking of MXene layers and enhance the active sites as compared to M–Cu2O. Regression equa-
tions for M–Cu2O and rGO–Cu2O are ΔI(µA) = 0.785 [Glucose] mM + 0.3623 with R2 = 0.99, ΔI (µA) = 1.174
[Glucose] mM + 0.5 with R2 = 0.97, respectively.
Moreover, CA response of the MG–Cu2O in glucose environment is divided into two sections of linearity
that is 0.01 to 10 mM and 11 to 30 mM with the slope value of 8.992 and 6.323, respectively. The correspond-
ing regression equations in these two sections are ΔI (µA) = 8.992 [Glucose] mM + 1.73 with R ­ 2 = 0.99 and ΔI
2
(µA) = 6.323 [Glucose] mM + 28.3 with ­R = 0.99. From these equations, a sensitivity of M–Cu2O, rGO–Cu2O
and MG–Cu2O is calculated and it given in Fig. 8d. A table of comparison of our material with the reported
ones is given in Table 1.
From Fig. 8d and Table 1, it could be understood that the prepared ternary composite (MG–Cu2O) is hav-
ing the enhanced sensitivity with a wide linear range of glucose sensing as compared to other sensing elements
(rGO–Cu2O and M–Cu2O). In these composites, a large surface area, high conductivity (6500 S ­cm−1) and
hydrophilicity nature of MXene sheet will increase the CuOOH formation in the electrolyte. It might generate
the enediol and lower the energy barrier of electrooxidation reaction with the addition of glucose to the elec-
trolyte. This will increase the number of electrons leading to a wide linear range as per the Yang et al.71. But the
sensitivity of the sensor was low as per the requirement for commercialization. Restacking of MXene sheet may
reduce the rate of electron transfer between the electrode and electrolyte. To prevent this, an incorporation of
rGO sheet (rGO will improve the rate of electron transfer process during the glucose ­sensor33) to MXene was
carried out. It will maintain the larger surface area of sheets as well as the ample amount of functional groups on
the surface and edges of sheet may hinder the nanoparticle agglomeration leading to the formation of spheri-
cal shape of C­ u2O in the MG–Cu2O composite, which further enhances the CuOOH formation and increases
the rate of electron transfer between electrode and electrolyte during the oxidation of glucose. In the prepared
ternary composites, MXene improves the linear range by a greater number of CuOOH formation and rGO will

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Figure 7.  A schematic showing the glucose sensing mechanism of MG–Cu2O composite.

improve the rate of electron transfer between the electrode and electrolyte. The combined role of MXene and
rGO has thus promoted the sensitivity of C­ u2O composite with wide linear range.

Interference, stability and reproducibility of MG–Cu2O modified electrode. To understand the

interference effect of MG–Cu2O composite, CA study was carried out with other interference species includ-
ing ascorbic acid, uric acid, lactose, fructose, sucrose, NaCl, KCl and urea along with glucose molecules. The
concentration of glucose and other interference species are used for this analysis as similar to the physiological
level of glucose in human ­blood64. From Fig. 9a, a massive and abrupt change in current was observed for the
glucose molecule as compared to other species. It indicates that the prepared composite is having a good anti-
interference effect. Moreover, stability and durability of MG–Cu2O modified electrode was carried out both by
chronoamperometry and cyclic voltammetry techniques.
A CV study was done in the presence of 10 mM glucose in the electrolyte for 100 cycles. It can be observed
from the inset of Fig. 9b, that even after 100 cycles, the peak current was maintained as similar to the initial
value. Along with this, CA test was carried out in the presence of glucose (1 mM) over time duration of 20 h. It
is observed from Fig. 9b that initially a huge change in current was observed with the addition of glucose and
gradually decreased over time due to the oxidation of glucose in the electrolyte. To confirm this phenomenon,
an equal amount of glucose was subsequently added to the electrolyte and the change of current is detected as
similar to the initial change, which indicates that the MG–Cu2O modified electrode has a good operational stabil-
ity. Furthermore, durability study was carried out by storing the modified electrode in ambient atmosphere for
30 days. To examine this, a change in current in 0.1 mM glucose is analyzed for two days once and then stored at
ambient atmosphere. This process is repeated until 30 days and then the activity loss of the device is evaluated and
given in Fig. 9c. After 30 days, only 10% of loss in the current from its initial value was observed, which signifies
the good durability of the prepared electrode. Moreover, the reproducibility of MG–Cu2O modified electrode
was examined by performing CA test with six different electrodes and demonstrated in Fig. 9d. A similar change
in current is observed in all the cases, which confirmed the reproducible nature of the sensing material.

Real time performance of MG–Cu2O modified electrode. To understand the real time application of
the prepared sensing electrode, the electrochemical test of the prepared sensing element in the presence of three
different serums was investigated. It was observed that the present sensing electrode shows 7.01 mM concen-
tration of glucose with the addition of serum 1, whereas it was found 7.15 mM concentration of glucose using
a commercial glucometer. A detailed relative standard deviation value between the proposed and commercial
glucometer is tabulated in Table 2. Lower value of deviation suggests that the prepared electrode is well suitable
for real time application with good reliability.

Conclusion
In this report, the role of graphene oxide in MXene–rGO composites is optimized and investigated as a sensing
probe for glucose sensing application. The optimized MG composite is later utilized to prepared the ternary
composite of rGO supported MXene based C ­ u2O composite (MG–Cu2O) by coprecipitation method. Structural

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Figure 8.  (a, b) Current versus time (Chronoamperometry) study of M–Cu2O and MG–Cu2O composite
with the successive addition of glucose at 0.6 V versus Ag/AgCl (inset—zoomed at lower concentrations) (c)
Comparative linear plot of MG–Cu2O and M–Cu2O composite (d) Sensitivity of prepared sensing materials.

Electrode Sensing method Linear range (mM) Detection limit (µM) Sensitivity (µAmM−1 ­cm−2) Ref
34
Cu2O/Au/GO NE Upto 16.65 0.83 2886
66
CuO/CG-GCE NE 0.1–3.17 0.01 1295
Cu NP on laser induced 67
NE 0.001–6 0.39 495
graphene
68
Ni/rGO/PU NE 0.01–2 1.28 4876
69
Cu-Co/rGO/PGE NE 0.001–4 0.15 240
65
S doped rGO/CuS NE 20.1 0.032 429
18
Pt-CuO-Pt NE 2.2–10 1.42 2921
70
Cu/rGO NE 0.1–12.5 65 172
43
GOx/Au/MX/Nafion E 0.1–18 5.9 4.2
33
NiO/Graphene NE 0.005–4.2 0.1 666.7
71
MXene/NiCo-LDH NE 0.002–4.096 0.53 64.75
44
MXene-Cu2O NE 0.01–30 2.83 11.064
Cu2O/rGO/MXene (MG-
NE 0.01–30 2.1 125.6 This work
Cu2O)

Table 1.  A comparison of glucose sensing performance of MG–Cu2O with others glucose sensors. *GCE
glassy carbon electrode, CG carboxylate graphene, PU polyurethane, PCE pencil graphite electrode, LDH
layered double hydroxide, NE non enzymatic, E enzymatic.

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Figure 9.  (a) Sensing analysis of respective elements in human serum for MG–Cu2O (0.5 mM glucose along
with 0.05 mM of other active species) (b) stability study of electrode in electrolyte using CV (inset) and CA (c)
storage stability of modified electrode with 0.1 mM of glucose (d) Sensing response of six different modified
electrodes with MG–Cu2O composite.

Concentration of glucose as sensed by

Serum Proposed sensor (mM) Commercial glucometer (mM) Relative standard deviations (RSD %)
1 7.01 7.15 1.4
2 5.71 5.89 2.19
3 6.1 6.31 2.39

Table 2.  Real time analysis of MG–Cu2O based electrode (Human serum).

analysis confirmed that the prepared composite is having high defect density with lower crystalline size as
compared to M–Cu2O composite. Such composites might lead to enhance the conductivity and amplifies the
signal towards glucose oxidation with MG–Cu2O as compared to M–Cu2O. Therefore, the prepared composite
shows a sensitivity of 125.6 µAmMcm−1 with a broad linear range (0.01 to 30 mM) and further it shows a good
selectivity, stability and reproducibility. Results show that the prepared MG–Cu2O composite is preferable for
analyzing the glucose level in human serum.

Data availability
All data generated or analysed during this study are included in this published article.

Received: 8 July 2022; Accepted: 18 November 2022

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Acknowledgements
The authors extend their appreciation to the Deputyship for Research & Innovation, Ministry of Education in
Saudi Arabia for funding this research work through the project no. (IFKSURG-2-975).

Author contributions
Conceptualization—T.G., A.N.G. Methodology—T.G., A.N.G. Validation—T.G., A.N.G. Formal analysis—
K.E.A., A.K.A., H.A., A.A., M.R.M., S.P. Investigation—A.N.G. Writing—Review and Editing—T.G., A.N.G.
Supervision—T.G., A.N.G. Project administration—K.E.A., A.K.A., H.A., A.A., M.R.M., S.P.

Competing interests
The authors declare no competing interests.

Additional information
Supplementary Information The online version contains supplementary material available at https://​doi.​org/​
10.​1038/​s41598-​022-​24700-w.
Correspondence and requests for materials should be addressed to A.N.G.
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Scientific Reports | (2022) 12:20583 | https://doi.org/10.1038/s41598-022-24700-w 15

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